Triazine derivatives



Patented Apr. 1, 1947 UNlTED STATES PATENT OFFICE TRIAZIN E DERIVATIVES Gaetano F. DAlelio and James W. Underwood, Pittsfield, Mass, assignors to General Electric Company, a corporation of New York No Drawing. Application August 19, 1942, Serial No. 455,357

substituted triazines.

The chemical compounds of this invention may be represented by the following general formula:

where n represents an integer and is at least 1 and not more than 3, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halo-hydrocarbon radicals, and R represents a member of the class consisting of monovalent aliphatic hydrocarbon radicals and monovalent aromatic and nuclearly substituted, specifically nuclearly halogenated, aromatic hydrocarbon radicals. From the above formula it will be noted that when n is 3 there will be no -NHR groups attached to the triazine nucleus.

Illustrative examples of radicals that R in the above formula may represent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl, hexyl, octyl, allyl, methallyl, crotyl, etc), including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc); aryl (e. g., phenyl, diphenyl or Xenyl, naphthyl, anthracyl, etc); aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropyl phenyl, allylphenyl, Z-butenylphenyl, propenylphenyl, tertiary-butylphenyl, methylnaphthyl, etc.) aryl-substituted aliphatic (e. g., benzyl, cinnamyl, phenylethyl, phenylpropyl, etc.); and their homologues, as Well as those groups with one or more of their hydrogen atoms substituted by, for example, a halogen, more particularly chlorine, bromine, fluorine or iodine. Specific examples of halogeno-substituted hydrocarbon radicals that R in the above formula may represent are: chloromethyl, chloroethyl, chlorophenyl, dichlorophenyl, ethyl chlorophenyl, chlorocyclohexyl, phenyl chloroethyl, bromo-ethyl, bromopropyl, fluorophenyl, iodophenyl, bromotolyl, etc. Preferably R is hydrogen.

Illustrative examples of monovalent aliphatic and aromatic hydrocarbon radicals that R in the above formula may represent are radicals such as above mentioned with reference to R. Illustrative examples of monovalent, nuclearly substitutedspecifically nuclearly halogenated,

aromatic hydrocarbon radicals that R also may represent are: chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, iodophenyl, fluorophenyl, chlorotolyl, bromotolyl, chloroxylyl, chloronaphthyL- dichloronaphthyl, chloroxenyl, dichlo-roxenyl, bromoxenyl and the like, Preferably R rep-resents a lower alkyl radical or a phenyl radical.

The new compounds of this invention may be used, for example, as pharmaceuticals, plasticizers and as intermediates in the preparation of derivatives thereof, e. g., methylol. methylene, etc., derivatives of the individual compound embraced by Formula I. These new compounds are especially valuable in the preparation of synthetic resinous compositions. Thus, they may be condensed with, for instance, aldehydes, including polymeric aldehydes, hydroxyaldehydes and. aldehyde-addition products, to yield condensation products of particular utility in the plastics and coating arts. Such condensation products are more fully described and are specifically claimed in our copending application Serial No. 455,356 filed concurrently herewith, now'U. S. 2,392,366, issued January 8, 1946, and assigned to the same assignee as the present invention. at

Various methods may be employed to produce the chemical compounds of this invention. One suitable method comprises effecting reaction. in the presence of a hydrohalide acceptor, between a triazine derivative corresponding to the general formula and an acyl halide corresponding to the general formula Illustrative examples of hydrazino-substituted triazines embraced by Formula II that may be employed, depending upon the particular endproduct sought, are:

Hydrazino diamino s-triazine (2-hydrazino 4,6-

diamino s-triazine; 4-hydrazino 2,6-diamino s-triazine; 6-hydrazino 2,4-diamino s-triazine) Z-hydrazino 4,6-di-(methy1amino) s-triazine Z-hydrazino 4,6-diethylamino) s-triazine Z-hydrazino 4-methylamino G-amino s-triazine 2-hydrazino 4-ethylamino 6-amino s-triazine Z-hydrazlno 4-methylamino 6-ethylamino s-triazine 2-hydrazino 4,6-di-(pentylamino) s-triazlne 2-hydrazino 4,6-di-(isobutylamino) s-triazine 2-hydrazino 4,6-di-(propenylamino) s-triazine 2-hydrazino 4,6-di-(butenylamino) s-triazine Z-hydrazino 4,6-di-(phenylamino) s-trazine Z-hydrazino 4,6-di- (chlorophenylamino) s-triazine 2hydrazino 4-anilino G-amino s-triazine 2-hydrazino 4-anilino fi-methylamino s-triazine 2-h'y'drazino 4.6-ditoluido s-triazine 2-hydrazino 4,6-dixy1id1no s-triazine Z-hydrazino 4,6-di-(naphthylamino) s-triazine 2-hydrazino 4,6-di-(ethylphenylamino) s-triazine 2-hydrazino4.6-di-(phenylethylamino) s-triazine 2-hydrazino 4.6-di-(cinnamylamino) s-triazine 2-hydrazino 4,6-di-(chloromethylamino) s-triazinei 2-hydrazino 4,6-di-Kbromoethylamino) s-triazine Z-hydrazino 4.6-di- (chloroanilino) s-triazine 2-hydrazino.4,6-di-(bromotoluido) s-triazine Di-hydrazino amino s-triazine Tri-hydrazino s-triazine 2,4-di-hydrazino G-methylamino s-triazlne 2,4-di-hydrazino 6-allyiamino s-triazine 2,4-di-hydrazino G-fluoroanilino s-triazine 2.4-di-hydrazino 6-iodoanilino s-triazine 2,4-di-hydrazino fi-cyclchexylamino s-triazine Illustrative examples of acyl halides that may be used, depending upon the desired end-product,

are: I

Various hydrohalide "acceptors may be employed but We prefer to use a tertiary base, e. g., tertiary amines such as trialkyl (e. g., trimethyl, triethyl, tripropyl, tributyl, etc.) amines, triaryl (e. g., triphenyl,.tritolyl, etc.) amines, Pyridine, dimethyl aniline, etc. The reaction between; the

hydrazino-substituted triazine and the acyl halide may be carried out in any suitable manner, but preferably is effected in the presence of a suitable solvent or mixture of solvents. It is ad-' visable to use an anhydrous medium, e. g., ether, benzene, toluene, etc., because of the high degree of reactivity of the acyl halide. The reaction may be carried out under a variety of temperature and pressure conditions, for instance at normal, sub-normal or at elevated temperatures and at atmospheric, sub-atmospheric or super-atmospheric pressures.

The above reaction may be represented by the following general equation:

n (hydrohalide acceptor) (BEN) a (salt of hydrohalide n acceptor) where X represents a halogen atom, and 1', R

and B hav the same meanings as given above.

- bers of the homologous series, e. g., the anhydrides of acetic, propionic, butanoic, butcnoic, isobutanoic, valeric, isovaleric, caproic, benzoic, chlorobenzoic, bromobenzoic, toluic, l-naphthoic and Z-naphthoic acids. This reaction preferably is carried out in a suitable solvent or mixture of solvents, e. g., ether, benzene, toluene, etc. The reaction conditions may be the same as described above with reference to the use of an acyl halide as a starting reactant, but ordinarily normal temperature and pressure conditions are preferred. The reaction may be represented'by the following general equation:

where n, R. and B have the same meanings as given above with reference to Formula I.

1 Another method that may be employedin preparing the new chemical compounds of-this in vention comprises effecting reaction between a halogenated triazine and a hydrazlde (aoyl hydrazine). This reaction preferably is carried out in the presence of a suitable solvent or mix ture of solvents. A hydrohalide acceptorial'so preferably is present. The reaction may be represented by the following general equation:

where X represents a halogen atom, and n, R and R have the same meanings as given above with referenc to Formula I. Preferably X is a chlorine or a bromine atom.

Another method that may be used in preparing compounds of this invention comprises effecting an addition reaction between (1) ketenes of the general formula R2-C=C=O, where R has the same meaning as given above with reference to Formula I and, in addition, hydrogen, and (2) a hydrazino-substituted triazine. This reaction may be represented by the following general equation:

0 N \N f n (RHN) n 6 -\-NH-NHCCHR'z where n and B hav the same meanings as given above with reference to Formula I, and R has the same meaning as given with reference to Formula I and, in addition, hydrogen.

In order that those skilled in the art better may understand how the present invention may be carried into effect, the following examples are given by way of illustration and not by way of limitation. All parts are by weight.

Example 1 This example illustrate the preparation of acetylhydrazino diamino s-triazine, the formula for which is VllI NH:

II A II H2N-C NH-NH C- C H:

Approx. Parts mol ratio Hydraziuo diamino s-triazine 100.0 1 Acetic anhydride 72. 4 1 Ethen. 150.0

The acetic anhydride was added slowly to the mixture of the other components. An exothermic reaction took place. After the reaction had subsided, the reaction fiask was stoppered and shaken for 6 hours at room temperature. After 6 standing for about 16 hours at room temperature; the precipitate comprising acetylhydrazino diamino s-triazine was filtered ofi, washed well with water and dried. A yield of 124 parts of the purified material Was obtained.

Example 2 Di-(acetylhydrazino) amino s-triazine is prepared in essentially the same manner as described under Example 1 with the exception that 110.6 parts of di-hydrazino amino s-triazine are used in place of parts of hydrazine diamino s-triazine and the amount of acetic anhydrideds increased from 72.4 to 144.8 parts. In other Words, reaction is effected between di-hydrazino amino s-triazine and acetic anhydride inthe ratio of one mol of the former to approximately two mols of the latter.

Example 3 Tri-(acetylhydrazino) s-triazine is prepared in essentially the same manner as described under Example 1 with the exception that 1212 parts of tri-hydrazino s-triazine are used in place of 100 parts of hydrazino diamino s-triazine and the amount of acetic anhydride is increased from 72.4 to 217.2 parts. In other words, reaction is efiected between tri-hydrazino s-triazine and acetic anhydride in the ratio of one mol of the former to approximately three mols of the latter.

Example 4 Acetylhydrazino di-(methylamino) s-triazine is prepared in essentially the same manner as described under Example 1 with the exception that 119.9 parts of hydrazine di-(methylamino) striazine are used in place of 100 parts of hydrazino diamino s-triazine.

Example 5 Propionylhydrazino diamino s-triazine is prepared in essentially the same manner as described under Example 1 with the exception that 92.3 parts of propi-onic anhydride are used instead of 72.4 parts of acetic anhydride.

Illustrative examples of other chemical compounds embraced by Formula I that may be produced in accordance with the present invention are listed below:

7 zeacetylhydrazino 4-ani1ino G-methylamino striazine Benzoylhydrazino diamino s-triazine Chlorobenzoylhydrazino diamino s-triazine Di-(benzoylhydrazino) amino s-triazine Tri-(benzoyihydrazino) s-triazine Toluylhydrazino diamino s-triazine Di-(toluylhydrazino) amino s-triazine Tri-(toluylhydrazino) s-triazine Dimethylbenzoylhydrazino diamino s-triazine Chlorobenzoylhydrazino di-(chloroethylamino) striazine Di-(benzoylhydrazino) methylamino s-triazine Di-(acetylhydrazino) benzoylhydrazino -stria- Zine Di-(acetylhydrazino) propionylhydrazino s-triazine Z-acetyihydrazino 4 benzoyihydrazino 6 propionylhydrazino s-triazine Acetylhydrazino di-(fiuoroanilino) s-triazine Propionylhydrazino di-(iodoaniiino) s-triazine Benzoylhydrazino di-(bromotoluido) s-triazine Bromohenzoylhydrazino di (bromoanilino) s triazine 1 Acetylhydrazino di-(chlorotoluido) s-triazine Acetylhydrazino di-(cyclohexyiamino) s-triazine Acetylhydrazino di-(octylamino) s-triazine 8 Acetylhydrazino di-(cyclohe'xenyiamino) 's-t'ri'a zine Acetylhydrazino di-(allylamino) s-triazine Di-propionylhydrazino) methallylamino s-triazine and acetic anhydride in approximately equi molecular proportions, allowing the reaction mass to remain undisturbed atiroom temperature and isolating and purifying the precipitate comprising acetylhydrazino diamino s-triazine.

GAETANO F. DALELIO. JAMES W. UNDERWOQD. 

